was obtained as long colourless needles, mp 201 ЊC (from
dichloromethane–light petroleum) with identical spectroscopic
properties to the above material.
J 7.1, H6), 6.92–7.04 (18H, m, Ar) and 7.16 (6H, dd, J 7.3 and
8.5, H5); δC (62.9 MHz; CDCl3) 20.8, 113.8, 121.9, 123.1, 124.6,
128.9, 129.7, 132.5, 144.7, 147.5 and 149.0; m/z 621 (Mϩ,
100%).
1,3,5-Tris(4-phenoxyphenylamino)benzene 17b. Anhydrous
phloroglucinol (3.0 g, 24 mmol), 4-phenoxyaniline (19.8 g, 108
mmol), iodine (0.10 g) and decalin were placed in a flask and
connected to a distillation apparatus. The reaction mixture was
heated with a sand bath at 190 ЊC for 8 h to drive off water.
After being allowed to cool the product was precipitated with
methanol and purified by flash chromatography on silica gel.
Ethyl acetate–light petroleum (20:80) eluted the title compound
(8.5 g, 57%) as purple flakes, mp 174–175 ЊC (from dichloro-
methane–methanol) (Found: C, 80.7, H, 5.0; N, 6.7. C42H33-
N3O3 requires C, 80.4; H, 5.3; N, 6.7%); λmax(HCCl3)/nm 299
(log ε 4.63); νmax (KBr)/cmϪ1 3382m, 3356m, 3035w, 1594s,
1503s, 1452m, 1392w, 1278m, 1228s, 1162m, 1106m, 1069w,
1017w, 868w, 852w, 816m, 794m, 747m and 692m; δH (250
MHz; CDCl3) 5.53 (3H, s, NH), 6.16 (3H, s, H1), 6.91–7.09
(21H, m, Ar) and 7.33 (6H, dd, J 7.3 and 8.5, H9); δC (62.9
MHz; CDCl3) 96.7, 118.0, 120.4, 121.4, 122.8, 129.7, 138.3,
146.4, 151.5 and 158.1; m/z 627 (100%).
1,3,5-Tris[(3,4-dimethylphenyl)phenylamino]benzene 3d. Yield
71%; colourless needles, mp 232–233 ЊC (from dichloro-
methane–methanol) (Found: C, 87.2; H, 6.8; N, 6.2. C48H45N3
requires C, 86.8; H, 6.8; N, 6.3%); λmax(HCCl3)/nm 306 (log
ε 4.79); νmax (KBr)/cmϪ1 3059w, 3014m, 2966m, 2916m, 2856m,
1578s, 1495s, 1461s, 1447s, 1298s, 1252s, 1210s, 1177m, 1145m,
1075w, 1045w, 1018w, 1000w, 902w, 813m, 764m, 715m, 692s
and 626m; δH (250 MHz; CDCl3) 2.16 (9H, s, Me), 2.20 (9H, s,
Me), 6.41 (3H, s, H1), 6.80 (3H, dd, J 2.2 and 8.1), 6.85–6.99
(9H, m, Ar), 7.02 (6H, dd, J 1.1 and 8.4, H4), 7.15 (6H, tt, J 7.3
and 8.5, H5); δC (62.9 MHz; CDCl3) 19.1, 19.9, 113.9, 121.7,
122.2, 123.2, 125.8, 128.8, 130.2, 131.2, 137.2, 145.0, 147.7 and
148.9; m/z 663 (Mϩ, 24%).
1,3,5-Tris[(3,5-dimethylphenyl)phenylamino]benzene 3e. Yield
69%; colourless solid, mp 208–209 ЊC (from dichloromethane–
light petroleum) (Found: C, 86.9; H, 6.6; N, 6.3. C48H45N3
requires C, 86.8; H, 6.8; N, 6.3%); λmax(HCCl3)/nm 306 (log
ε 4.79); νmax (KBr)/cmϪ1 3032m, 2950m, 2915m, 2858m, 1576s,
1489s, 1465s, 1440s, 1379m, 1329s, 1273m, 1245s, 1203s, 1155m,
1072m, 1029m, 870w, 838w, 804w, 766m, 729w and 701s; δH
(250 MHz; CDCl3) 2.19 (18H, s, Me), 6.42 (3H, s, H1), 6.58
(3H, s, H10), 6.65 (6H, s, H8), 6.91 (3H, t, J 7.3, H6), 7.02 (6H,
d, J 8.6, H4) and 7.16 (6H, dd, J 7.3 and 8.5, H5); δC (62.9
MHz; CDCl3) 21.4, 114.8, 121.8, 122.2, 123.7, 124.5, 128.9,
138.5, 147.1, 147.6 and 148.9; m/z 663 (Mϩ, 100%).
General procedure: 1,3,5-tris(diphenylamino)benzene 3a
A method similar to that reported previously was used but
with the following modifications and improvements: 1,3,5-tris-
(phenylamino)benzene (2.0 g, 6.0 mmol), iodobenzene (6.97 g,
34 mmol), crushed KOH pellets (3.83 g, 68 mmol), copper
bronze (2.6 g) and n-decane as solvent were added to a two
necked flask equipped with a water condenser and nitrogen
supply. The reaction mixture was refluxed with a sand bath for
24 h or until only one product spot could be detected by TLC.
The reaction mixture was then allowed to cool followed by the
addition of methanol (50 cm3) which precipitated the crude
product. The solid was filtered off, dissolved in CH2Cl2 and
filtered to remove inorganic residues. The product was purified
by flash chromatography on silica gel. Light petroleum–
dichloromethane (85:15) eluted the title compound (2.25 g,
68%) as colourless needles, mp 259–260 ЊC (lit.,5a 257 ЊC) (from
dichloromethane–methanol) (Found: C, 86.8; H, 5.5; N, 7.2.
C42H33N3 requires C, 87.0; H, 5.7, N, 7.3%); λmax(HCCl3)/nm
304 (log ε 4.75); νmax (KBr)/cmϪ1 3057w, 3029w, 1577s, 1490s,
1464s, 1437m, 1318m, 1286m, 1243s, 1171m, 1148m, 1074w,
1036w, 830w, 754m, 695s, 631m and 620m; δH (250 MHz;
CDCl3) 6.42 (3H, s, H1), 6.91 (6H, tt, J 1.3 and 7.1, H6), 7.03
(12H, dd, J 1.2 and 8.3, H4) and 7.16 (12H, m, H5); δC
(62.9 MHz; CDCl3) 114.5, 122.6, 124.0, 129.0, 147.4 and 149.1;
m/z 579 (Mϩ, 100%).
1,3,5-Tris[(2,4-dimethylphenyl)phenylamino]benzene 3f. Yield
53%; colourless solid, mp 87 ЊC (from dichloromethane–
methanol) (Found: C, 87.0; H, 6.6; N, 6.3. C48H45N3 requires C,
86.8; H, 6.8; N, 6.3%); λmax(HCCl3)/nm 301 (log ε 4.97); νmax
(KBr)/cmϪ1 3033m, 1583s, 1493s, 1464s, 1442s, 1294s, 1253s,
1228s, 1159w, 739m and 692s; δH (250 MHz; CDCl3) 1.91 (9H,
s, Me), 2.28 (9H, s, Me), 6.12 (3H, s, Ar), 6.82–6.91 (18H, m,
Ar) and 7.03–7.09 (6H, t, J 7.5 and 7.5); δC (62.9 MHz; CDCl3)
18.3, 21.0, 109.2, 120.3, 127.8, 128.6, 129.2, 132.0, 135.5, 136.1,
142.4, 147.2 and 148.1; m/z 663 (Mϩ, 100%).
1,3,5-Tris[(3-chlorophenyl)phenylamino]benzene 3g. Yield
30%; colourless solid, mp 176–177 ЊC (from dichloromethane–
light petroleum) (Found: C, 73.04; H, 4.25; N, 6.22. C42H30-
N3Cl3 requires C, 73.9; H, 4.4; N, 6.2%); λmax(HCCl3)/nm 302
(log ε 4.93); νmax (KBr)/cmϪ1 3057m, 3035m, 1583s, 1565s,
1493s, 1473s, 1423m, 1283s, 1239s, 1150m, 1076m, 947w, 759s
and 701s; δH (250 MHz; CDCl3) 6.37 (3H, s), 6.85–6.88 (6H, d,
J 7.5), 6.95–7.10 (15H, m) and 7.19–7.25 (6H, t, J 7.5 and
7.5); δC (62.9 MHz; CDCl3) 114.6, 121.2, 122.4, 123.0, 123.8,
124.8, 129.4, 130.0, 134.6, 146.4, 148.6 and 148.7; m/z 682
(Mϩ, 100%).
1,3,5-Tris[(3-methylphenyl)phenylamino]benzene 3b. Yield
72%; colourless solid, mp 183–184 ЊC (lit.,5a 183 ЊC) (from
dichloromethane–methanol) (Found: C, 86.9; H, 6.3; N, 6.5.
C45H39N3 requires C, 86.9; H, 6.3; N, 6.8%); λmax(HCCl3)/nm
304 (log ε 4.74); νmax (KBr)/cmϪ1 3060w, 3030m, 2949w, 2919w,
2858w, 1579s, 1489s, 1461s, 1294s, 1254s, 1189m, 1170m,
1043w, 893w, 801w, 778m, 757m, 723w, 694s, 651w and 627w;
δH (250 MHz; CDCl3) 2.22 (9H, s, Me), 6.43 (3H, s, H1), 6.73–
7.20 (27H, m, Ar); δC (62.9 MHz; CDCl3) 21.5, 114.6, 121.2,
122.4, 123.5, 123.9, 124.5, 128.9, 129.0, 138.8, 147.2, 147.4 and
149.0; m/z 621 (Mϩ, 100%).
1,3,5-Tris[(3-methylphenyl)(4-phenoxyphenyl)amino]benzene
3h. The same general procedure above was followed but 1,3,5-
tris(4-phenoxyphenylamino)benzene 17b was used in place of
1,3,5-tris(phenylamino)benzene 17a. Yield 51%; colourless
needles, mp 153–154 ЊC (from dichloromethane–methanol)
(Found: C, 84.0; H, 5.4; N, 4.7. C63H51N3O3 requires C, 84.3; H,
5.7; N, 4.7%); λmax(HCCl3)/nm 307 (log ε 4.84); νmax (KBr)/cmϪ1
3037m, 2918w, 2861w, 1588s, 1573s, 1501s, 1487s, 1462s,
1306m, 1290m, 1259s, 1228s, 1191s, 1163m, 870m, 837m, 780m,
749m, 729m and 691s; δH (250 MHz; CDCl3) 2.22 (9H, s, Me),
6.33 (3H, s, H1), 6.73 (3H, d, J 7.0), 6.86–7.10 (30H, m, Ar) and
7.32 (6H, dd, J 7.5 and 8.3); δC (62.9 MHz; CDCl3) 21.6,
112.3, 118.4, 119.8, 120.6, 123.0, 124.0, 126.3, 128.8, 129.7,
138.7, 143.0, 147.3, 149.1, 152.5 and 157.7 (one overlapping
resonance); m/z 663 (Mϩ, 100%).
1,3,5-Tris[(4-methylphenyl)phenylamino]benzene 3c. Yield
49%; colourless needles, mp 214–215 ЊC (lit.,5a 198 ЊC) (from
dichloromethane–methanol) (Found: C, 87.4; H, 6.2; N, 6.6.
C45H39N3 requires C, 86.9; H, 6.3; N, 6.8%); λmax(HCCl3)/nm
304 (log ε 4.74); νmax (KBr)/cmϪ1 3060w, 3030w, 2920w, 2858w,
1579s, 1507s, 1464m, 1444m, 1315m, 1287s, 1247s, 1176w,
1146w, 1112w, 1037w, 816m, 722m, 694m and 614w; δH (250
MHz; CDCl3) 2.29 (9H, s, Me), 6.41 (3H, s, H1), 6.89 (3H, t,
2700
J. Chem. Soc., Perkin Trans. 1, 2000, 2695–2701